Production of sulphone-ethylamines



Patented Dec. 20, 1938 v UNITED STATES PATENT" OFFICE .ml fiifilhffiama.

'manmasaignor to I. G. I'arbenlndustrle Ak- I'rankfort-on-tho-Iain, Gae-No Drawing. Application/January 84,108., 80- No. 60,633; In GermanyJanuary 31,-1.8!

Thespresent invention relates to sulphoneheterocyclicoompolmdaaralkylamines (phenyletiwlamines and a process ofproducingsame. ethylamine) and cycloaiiphaticamines (cyclor A processfor theproduction of-organic sulphur hexylamine) and their mono-N-aikyl,hydroxycompoundsis described in application Ser. No. alkyl, aryl, aralhland a'cyi compounds. Fur- '26,091, filed on Junev 11th, 1935 accordingto m m compound; hgvl at least ne which compounds of thegenei'al formulaNH-group gomblned 1n the form of a ring, as for a v example piperidineor carbaaole, may be em- (in which X stands for -SO--- or SO' a, R for:Sgh f gj fg f mg' m ggg 1 22 10 an alkenylqgroup and R, for an organicradicie) or m hydroxyml mhydroxyl or are reacted with compoundscontaining at least hexyhe em, group fm compounds o 1 one nitrogen atomcombined with one or more taming oxygen or an group directly attachedhydrogen to the nitrogen atom bearing at least one reactive I have nowfound that sulphone-ethylamines hydrogen atom arehettehe employed 1 canalso be obtained in very good yields by caus- The reaeheh tempemmregenemfiy speaking ing acetylene to act at elevated temperatures onbetween about end about 5 usuauy mixtures of sulphinic acids andcompounds which tween and By reason, the fact contain at least-onenitrogen atom to which at that the eulphime acid are 1 not volatileleast one hyd e t is directly attachedwithout decompofltion the reactionis preferably The reaction may be carried out in the absence can-led outin the liquid phase solvents or m- 2 of catalysts, but is preferablycarried out in the neat; sueh as alcohol, hetenee ethers orhydropresence of catalysts. As such catalysts may be eel-hobs, may alsohe avantegeausly emp1oyed mentioned .in particular basic substances, asfor w the honing point of the components example the oxides, hydroxides,cyanides, aimite, the preeees may he earned t at atmescoholates,phenolates and naphtholates of the n preeeure but in My all cases it isrefalkali metals? and the ides zinc Ind erable to work at increasedpressure because the 25 cadmium. The 0f the Said metals of reaction isthereby considerably organic acids, as for example their acetates, areereaeed A eumelent dilution f the acetylene "3130' suitable ascatalysts. There may also be inert ga es such nitrogen or ethane isadded to the catalysts, mercury compounds, as then 11mm! forexamplemercuric oxide, sulphate or phos- The process may he earned u dlscontmwphate. Boron fluoride may also be present. The ously. or eonunueusm Inthe latter case it is 7 catalysts usually allow to employ somewhat lowerpreferable Dream-e418! tower capable temperatures. -Anaccelerationin-the absorption of being heated and if desired eepable'ofbeing of acetylene. is obtained also when substances cooled which isehmiged with h initial mixture having large surfaces, as for exampleactive carheated to ti temperature, acetylene,

' 0 (ethylamine, propylamine, butylamine, octodecyibon, fuliers-earth orsilica gel, are added to the for example then being led upwards throughmmal mixturei the tower; 1r desired after dilution with inert Thereaction m be carried out w th gases. The unconverted acetylene ispreferably basic or polybasic aliphatic or aromatic, sulphinic returnedto the tower The smphone ethymmme 40 acids. The sulphinic acids maycontain further formed 8 withdrawn ontmuously from the upper atomsatomic groups as for example halogen end of the towerwhile fresh initialmixture toatoms, acid *radicles, or alkyl,'. hydroxyalkyl, alkoxy, nitroor substituted amino groups, pro- 5:2 ggg f is continuously introducedvided the said acids are stable under the reaction conditions. Ascompounds containing at least one nitrogen atom to which at least onereactive hydrogen atom is directly attached, may be mentioned forexample ammonia, primary and secondary alkylamines andhydroxyalkylamines The suiphone-ethyla mines obtained may be used forexample for the preparation ofdyestuffs, as assistants for the textileand related industries or, when appropriate initial materials areemployed, as dyestufls themselves.

The following examples will further illustrate the nature of thisinvention but the invention is not restricted to these examples.v Theparts are by weight.

amine, octodecenylamine and monoand dihydroxyethylamines), primary andsecondary aromatic amines (aniline, phenylene diamine, naphthylamine andaminoanthraquinone),mono- Example 5s amines -or "polyamines-ofother'isocyclic and eAgas mixture of nitrogen and acetylene in ized fromtime to time by the addition of high- I percentage acetylene. Afterabout 15 hours, the calculated amount of acetylene has been absorbed'andthe whole is allowed to cool.

After distilling oil? the. xylene under reduced pressure, there remainabout 27 parts of a thick yellow oil which mainly consists of thecompound:

It may be precipitated in the form of its oxalic acid salt bydissolution in ethanol and addition of a solution of anhydrous oxalicacid in ethanol, and may then be purified by crystallization fromethanol. The oxalic acid salt forms colorless crystals which melt atabout 160 'C.

The same compound is obtained by employing as catalyst 1.5 parts ofpowdered potassium hydroxide instead of zinc oxide and cadmium oxide andby working at a somewhat higher temperature (about 160 C.). Instead ofxylene, other solvents, as for example butanol, may be em-' ployed.

The same compound isv also obtained without 7 any catalyst, but thereaction in this case proceeds much more slowly, even at highertemperature (180 0.).

If, instead of diethylamine, 15.6 parts of monoethyl aniline beemployed, there is obtained the sulphone-ethylamine of the formula:

CzHt

which forms colorless crystals melting at from 71 to 72 C. If, insteadof para-toluene sulphinic acid, one employs benzene sulphinic acid,there is obtained the sulphone-ethylamine of .the formula:

Example 2 age acetylene until the necessary amount of by crystallizationfrom ethanol.

acetylene has been absorbed, which usually requires about 16 hours.

After distilling 01f the xylene under reduced.

pressure, the residue is extracted while hot with dilute aqueoushydrochloric acid and the hydrochloric acid solution is evaporated underreduced pressure. The hydrochloride compound, which has the formula:

' CHz-CH:

oral-on,

remains behind. It is obtained in the pure form It forms colorlesscrystals which melt at 226 C.

If the piperidine be replaced by 3 parts of gaseous ammonia; thebis(beta-para-tolyl-sulphone-ethyl) amine having the formula:

is obtained, the hydrochloride of which forms colorless crystals whichmelt at from 200 to 201 0., andwhich maybe well crystallized from wateror ethanol. Other sulphinic acids and other compounds containing atleast one nitrogen atom' combined with one or more hydrogen atoms yieldsthe corresponding sulphone-ethylamines in a similar manner.

Example 3 Acetylene is caused to react in the manner described in thepreceding examples with a mixture of 250 parts of para-toluene sulphinicacid ammonium salt, 300 parts of butanol, 5 parts of anhydrous ammoniaand 8 parts of potassium hydroxide in a pressure-vessel provided with astirrer. Any undlssolved parts are separated 011, the liquid is renderedacid to Congo and the solvent is distilled off. The residue consists ofthe hydrochloric acid salt of bis-(p-para-tolylsulphonethyDamine whichmay be purified by trituration with acetone and recrystallization fromwater or alcohol. The product consists of colorless crystals melting atfrom 200 to 201 0.

Example 4 300 parts of para-toluene sulphinic acid phenylhydrazine aremixed with 1500 parts of xylene and 1000 parts of the latter aredistilled on whereby practically all the water present is removed. 10parts of phenylhydrazine, parts of potassium hydroxide, 5 parts of zincoxide and 5 parts of cadmium oxide are added and the mixture obtained istreated at from 155 to 165 C. with acetylene in the manner described inExamples 1 and 2.

After cooling the undlssolved parts are removed and the solution isfreed from the solvent at about 100 C. under reduced pressure. Theresidual oil is dissolved in alcohol. By the addition of anhydrousoxalic acid the oxalic acid salt of the reaction product is precipitatedin colorless crystals which after one recrystallization from ethanolmelt at about 155 C. In contrast to oxalic acid phenylhydrazine salt itis readily soluble in-hot alcohol.

Example 5 A mixture of 300 parts of 1.3-benzenedisul-. phinic aciddiethylamine iH5)I=NH.H0zS

- 8 0zH.NH=(C2Hn)2 500 parts of xylene, parts of diethylamine of the newand parts of potassium hydroxide is treated with acetylene at from 155to 160 C. in the manner described in Examples 1 and 2. After cooling theundissolved parts are removed and the solution is freed from volatileparts by distillation under reduced pressure at about 100 C.

cording to analysis and its properties corresponds to the formula formscolorless crystals melting at from 143 to 145 C. and which arediflicultly soluble in acetone, soluble in warm ethanol and readilysoluble in water.

If instead of 1.3-benzenedisulphinic acid diethylamine the compounda.p-ethanedisulphinic acid diethylamine is employed,ethylene-blusdiethylaminoethyl-sulphone) is obtained in an .analogousmanner; it is an oil soluble in ethanol.

What I claim is:-

l. The process for producing sulphone-ethylamines, which comprisescausing acetylene to act at a temperature between about 50 and about 250C. on a mixture of a sulphinic acid selected from the group consisting01' alkyl sulphinic acids and sulphinic acids of the benzene series andan amine selected from the groupconsisting of primaryand secondaryamines which are free from act in the liquid phase at a temperaturebetween about 50 C. and about 250 C. in the presence of a basicreacting, metal compound on a mixture of a sulphinic acid selected fromthe group consisting of alkyl sulphinic acids and sulphinic acids of thebenzene series and an amine selected from the group consisting ofprimary and secondary amines which are free from oxygen and acyl groups.

4. The process for producing sulphone-ethylamines, which comprisescausing acetylene to act in the liquid phase at a temperature betweenabout C. and C, in the presence of a basic reacting, metal compound on amixture of a sulphinic acid selected from the group consisting of alkylsulphinic acids and sulphinic acids of the benzene series and an amineselected from the group consisting of primary and secondary amines whichare free from oxygen and acyl groups.

5. The process for producing sulphone-ethylamines, which comprisescausing acetylene to act in the liquid phase at a temperature betweenabout 50 C. and about 250 C. in the presence of a basic reacting, metalcompound and of a diluent on a mixture of a sulphinic acid selected fromthe group consisting or alkyl sulphinic acids and sulphinic acids of thebenzene series and an amine selected from the group consisting ofprimary and secondary amines which are free from oxygen and acyl groups.

6. The process for producing'sulphone-ethylamines, which comprisescausing acetylene to act at a temperature between about 50 C. and about250 C. on a mixture of a sulphinic acid of the benzene series and asecondary amine which is free from oxygen and acyl groups.

'7. The compound corresponding to the formula CaHl

HANNS UFER.

